Structural Evolution and Properties of Praseodymium Antimony Oxochlorides Based on a Chain-like Tertiary Building Unit

Abstract

Unveiling the structural evolution of single-crystalline compounds based on certain building units may help greatly in guiding the design of complex structures. Herein, a series of praseodymium antimony oxohalide crystals have been isolated under solvothermal conditions via adjusting the solvents used, that is, [HN(CH2CH3)3][FeII(2,2′-bpy)3][Pr4Sb12O18Cl15]·EtOH (1) (2,2′-bpy = 2,2′-bipyridine), [HN(CH2CH3)3][FeII(2,2′-bpy)3]2[Pr4Sb12O18Cl14)2Cl]·N(CH2CH3)3·2H2O (2), and (H3O)[Pr4Sb12O18Cl12.5(TEOA)0.5]·2.5EtOH (3) (TEOA = mono-deprotonated triethanolamine anion). Single-crystal X-ray diffraction analysis revealed that all the three structures feature an anionic zig-zag chain of [Pr4Sb12O18Cl15−x]n as the tertiary building unit (TBU), which is formed by interconnections of praseodymium antimony oxochloride clusters (denoted as {Pr4Sb12}) as secondary building units. Interestingly, different arrangements or linkages of chain-like TBUs result in one-dimensional, two-dimensional layered, and three-dimensional structures of 1, 2, and 3, respectively, thus demonstrating clearly the structural evolution of metal oxohalide crystals. The title compounds have been characterized by elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and UV-Vis spectroscopy, and the photodegradation for methyl blue in an aqueous solution of compound 1 has been preliminarily studied. This work offers a way to deeply understand the assembly process of intricate lanthanide-antimony(III) oxohalide structures at the atomic level.

Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds

“…Their susceptibility increased with decreasing temperature and no peaks were detected down to 2 K, indicating a paramagnetic behavior at low temperature. It is noted that the susceptibility between 2 and 300 K could be well-fitted with the Curie-Weiss law χ = χ 0 + C/(T − θ CW ) above 100 K, giving χ 0 = 0.0049 (8)…”

“…Thus, it is crucial to solve the environmental pollution problems caused by these species [25][26][27]. In recent years, a number of scholars have utilized metal oxides with precise atomic structures as catalysts for photodegradation of organic dye wastewater [8,28,29]. On account of this, we investigated the photocatalytic degradation performance of compounds 2 and 4 as inhomogeneous reaction photocatalysts using methylene blue (MB) as a simulated pollutant.…”

“…The design and synthesis of organic-inorganic hybrid compounds based on Sb(III)-oxo clusters have drawn increasing attention recently. The organic components may play two roles in these hybrids, that is, acting as charge-balancing cations or as ligands entering or linking the Sb(III)oxo-based clusters [7][8][9][10][11][12][13][14][15]. In the synthesis of these hybrids, potassium antimony tartrate has been widely favored by scholars for its feature of undergoing decomposition and rearrangement in water to form {Sb 3 (µ 3 -O)(tta) 3 } scaffolds with three bridging oxygen groups, which further capture other metal ions to form a cluster-based structure [13,16].…”

Mixed-valence compounds based on heterometallic-oxo-clusters containing Sb(iii,v): crystal structures and proton conduction

“…13–15 For instance, our group has successfully integrated Sb 3+ with Pr 3+ ions to design and synthesize a series of {Pr 4 Sb 12 } oxochloride cluster-based structures. 16–21…”